JPH0943794A - Heat-developable color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the heat-developable color photosensitive material capable of forming an image superior in color repro-ducibility and discrimination and superior in storage stability of raw stock. SOLUTION: The heat-developable color photosensitive material comprises a support, and a reducible dye donor, a binder, an electron transfer agent, an electron donor, a reducible dye donor, and a compound of formula I or its precursor selected from formulae II and III, and in formulae I-III, Dye is a dye group represented by formula IV or its precursor; Y is a group to be released in reverse accordance with reduction of photosensitive silver halide having an imagewise formed latent image and to give difference on diffusibility of a group functioning as a development inhibitor; (p) is an integer of >=1; (q) is 1 or 2; and when (p) is >=2 or (q) is 2, each of Dye or (Dye)p -X may be same or different from each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-development color light-sensitive material having excellent color reproducibility and good discrimination.

[0002]

2. Description of the Related Art Photothermographic materials are well known in this technical field, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering", Non-silver photography (edited in 1982, page 242). Page 255, U.S. Pat. No. 4,500,626.

[0003] Many methods have been proposed for obtaining a color image by thermal development. For example, U.S. Patent No.
No. 3,531,286, No. 3,761,270, No. 4,021,240, Belgian Patent No. 802,519, Research Disclosure Magazine (hereinafter abbreviated as RD), September 1975, pages 31 to 32, etc. A method of forming a color image has been proposed.

Many methods have been proposed for obtaining a positive color image by heat development. Among them, in U.S. Pat. No. 4,559,290, a so-called DRR compound is present in the presence of an oxidized compound having no color image releasing ability and a reducing agent or a precursor thereof, and the reducing agent is added according to the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by oxidizing the dye and reducing it with a reducing agent remaining without being oxidized. In addition, European Patent Publication 220,746, JP-A 64-1354
No. 6 discloses a compound that releases a diffusible dye by the same mechanism as a compound that releases a diffusible dye by reductive cleavage of an N—X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom). A heat-developable color light-sensitive material using is described.

[0005]

In recent years, various attempts have been made to improve the color reproducibility of images. In the light-sensitive material as described above, in order to improve the color reproducibility of the image,
The spectral sensitivity of each photosensitive silver halide may be sharpened, or color formation or inhibition of color formation due to a side reaction of an adjacent layer may be prevented. In order to avoid the influence of the adjacent layer, there is a method of increasing the film thickness of the layer in which the coloring reaction does not occur, but this causes a decrease in the maximum density, which is a problem. Further, changing the spectral sensitivity of the photosensitive silver halide causes a problem such as sensitivity fluctuation. Therefore, it has been desired to develop a heat-developable color light-sensitive material that improves color reproducibility and does not cause these problems.

Therefore, the object of the present invention is to obtain excellent color reproducibility,
An object is to provide a heat-developable color light-sensitive material having good discrimination.

[0007]

As a result of research to solve the above-mentioned object, the present inventor has found that the following light-sensitive material achieves the object. In addition to the above objects, the present invention has also found that the photographic material is excellent in raw storage stability.

At least a photosensitive silver halide, a binder, an electron transfer agent and / or a precursor thereof, an electron donor and / or a precursor thereof, and a reducible dye which is reduced to release a diffusible dye on a support. A heat-developable color light-sensitive material having at least one layer containing a donating compound, having a layer containing at least one compound represented by the following general formula [I], and the same layer and / or Alternatively, a heat-developable color light-sensitive material comprising another layer containing at least one compound represented by the following general formulas [II] and [III].

[0009]

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[0010]

[Chemical 6]

[0011]

[Chemical 7]

In the general formula [I], Dye is represented by the following general formula [I
V] represents a dye group or dye precursor group. Y is a group having a property of causing a difference in diffusivity of a group functioning as a development inhibitor after the photosensitive silver halide having an imagewise latent image is released corresponding to reduction to silver. And X represents a simple bond or a linking group. p represents a natural number of 1 or more, and q represents 1 or 2. When p is 2 or more or q is 2, Dye or (Dye) _p −X
May all be the same or different.

[0013]

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In the formula, R ₁ and R ₂ are each independently a hydrogen atom,
Halogen atom, hydroxyl group, cyano group, nitro group, carboxyl group, substituted or unsubstituted, alkyl group, aralkyl group, cycloalkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group, acylamino group, Sulfonylamino group, acyl group, sulfonyl group,
It represents a substituent selected from a carbamoyl group, a sulfamoyl group, a ureido group, an alkylthio group and an arylthio group. R ₃ has the same meaning as R ₁ and R ₂ except for the hydrogen atom defined by R ₁ and R ₂ . n represents an integer of 0 to 5,
When n is 2 to 5, R ₃ may be the same or different. Dye and X are bonded via any _one of R ₁ , R ₂ and R _{3 in} the general formula [IV].

The compounds of the general formulas [II] and [III] are known compounds as sulfonic acid ester and carboxylic acid ester, respectively, and in the present invention, these compounds are used as acid precursors. Here, the acid precursor is defined as a compound that releases an acid by heat or hydrolysis.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The compound of the formula [I] will be described in more detail. X is a bond or a linking group, and when X is a linking group, an alkylene group, a substituted alkylene group,
Arylene group, substituted arylene group, heterocyclic group, -O
_{-, - SO 2 -, -} CO -, - NR 14 - (R 14 is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group.)
, And groups represented by a combination of two or more thereof.

A preferred linking group is --NR ¹⁴ SO
^{_{2 -, - NR 14 CO -}} , - O -, - SO 2 - and, also these with a substituted or unsubstituted alkylene group (e.g. methylene, ethylene, propylene, etc.), an arylene group (e.g. o- phenylene, m- phenylene , P-phenylene,
1,4-naphthylene and the like).

When X has a substituent, a preferred substituent is an alkyl group (an alkyl group which may be substituted. For example, methyl, trifluoromethyl, chloromethyl, dimethylaminomethyl, ethoxycarbonylmethyl, aminomethyl, acetyl). Aminomethyl, ethyl, carboxyethyl, 3,3,3-trichloropropyl, n-propyl, iso-propyl, n-butyl, iso-butyl,
sec-butyl, t-butyl, n-pentyl, sec-
Pentyl, t-pentyl, cyclopentyl, n-hexyl, sec-hexyl, t-hexyl, cyclohexyl, n-octyl, sec-octyl, t-octyl,
n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, se
c-hexadecyl, t-hexadecyl, n-octadecyl, t-octadecyl, etc.), aralkyl group (optionally substituted aralkyl group, for example, benzyl, etc.)

Alkenyl group (Alkenyl group which may be substituted. For example, vinyl, allyl, 2-chlorovinyl, 1
-Methyl vinyl, 2-cyano vinyl, cyclohexene-
1-yl, etc., alkynyl group (optionally substituted alkynyl group. For example, ethynyl, 1-propynyl, 2-
Ethoxycarbonylethynyl, etc.),

Aryl group (an optionally substituted aryl group. For example, phenyl, naphthyl, 3-hydroxyphenyl, 3-chlorophenyl, 4-acetylaminophenyl, 2-methanesulfonyl-4-nitrophenyl, 3-
Nitrophenyl, 4-methoxyphenyl, 4-acetylaminophenyl, 4-methanesulfonylphenyl, 2,
4-dimethylphenyl, etc.),

Heterocyclic group (an optionally substituted heterocyclic group. For example, 1-imidazolyl, 2-furyl, 2-pyridyl, 5-nitro-2-pyridyl, 3-pyridyl, 3,
5-dicyano-2-pyridyl, 5-tetrazolyl, 5-
Phenyl-1-tetrazolyl, 2-benzthiazolyl,
2-benzimidazolyl, 2-benzoxazolyl, 2
-Oxazolin-2-yl, morpholino, etc.),

Acyl group (acyl group which may be substituted; for example, acetyl, propionyl, butyroyl, iso-
Butyroyl, 2,2-dimethylpropionyl, benzoyl, 3,4-dichlorobenzoyl, 3-acetylamino-4-methoxybenzoyl, 4-methylbenzoyl, 4
-Methoxy-3-sulfobenzoyl, etc.),

Sulfonyl group (an optionally substituted sulfonyl group, for example, methanesulfonyl, ethanesulfonyl,
Chloromethanesulfonyl, propanesulfonyl, butanesulfonyl, benzenesulfonyl, 4-toluenesulfonyl, etc.), carbamoyl group (optionally substituted carbamoyl group, for example, carbamoyl, methylcarbamoyl, dimethylcarbamoyl, bis- (2-methoxyethyl)). Carbamoyl, dimethylcarbamoyl, cyclohexylcarbamoyl, etc.), sulfamoyl group (optionally substituted sulfamoyl group, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl,
Diethylsulfamoyl, bis- (2-methoxyethyl) sulfamoyl, di-n-butylsulfamoyl,
3-ethoxypropylmethylsulfamoyl, N-phenyl-N-methylsulfamoyl, etc.),

Alkoxy or aryloxycarbonyl groups (optionally substituted alkoxy or aryloxycarbonyl groups, such as methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, 2-methoxyethoxycarbonyl, etc.), alkoxy or aryloxysulfonyl groups (substituted) Optionally alkoxy or aryloxysulfonyl groups, such as methoxysulfonyl, ethoxysulfonyl, phenoxysulfonyl, 2-methoxyethoxysulfonyl, etc.),

Alkoxy or aryloxy group (optionally substituted alkoxy or aryloxy group.
For example, methoxy, ethoxy, methoxyethoxy, 2-
Chloroethoxy, phenoxy, p-methoxyphenoxy and the like), alkylthio or arylthio group (optionally substituted alkylthio group or arylthio group. For example, methylthio, ethylthio, n-butylthio, phenylylthio, 4-chlorophenylthio, 2-methoxyphenyl. Thio, etc.),

Amino group (optionally substituted amino group, for example, amino, methylamino, N, N-dimethoxyethoxyamino, methylphenylamino, etc.), ammonio group (optionally substituted ammonio group, for example, ammonio, Trimethylammonio, phenyldimethylammonio, dimethylbenzylammonio, etc.),

Acylamino group (acylamino group which may be substituted. For example, acetylamino, 2-carboxybenzoylamino, 3-nitrobenzoylamino, 3
-Diethylaminopropanoylamino, acryloylamino and the like), an acyloxy group (an optionally substituted acyloxy group, for example, acetoxy, benzoyloxy, 2
-Butenoyloxy, 2-methylpropanoyloxy, etc.),

A sulfonylamino group (an optionally substituted sulfonylamino group. For example, methanesulfonylamino,
Benzenesulfonylamino, 2-methoxy-5-n-methylbenzenesulfonylamino, etc.),

Alkoxycarbonylamino group (Alkoxycarbonylamino group which may be substituted. For example, methoxycarbonylamino, 2-methoxyethoxycarbonylamino, iso-butoxycarbonylamino, benzyloxycarbonylamino, t-butoxycarbonylamino, 2- Cyanoethoxycarbonylamino), an aryloxycarbonylamino group (an optionally substituted aryloxycarbonylamino group, for example, phenoxycarbonylamino, 2,4-nitrophenoxycarbonylamino, etc.),

Alkoxycarbonyloxy group (alkoxycarbonyloxy group which may be substituted. For example, methoxycarbonyloxy, t-butoxycarbonyloxy, 2-benzenesulfonylethoxycarbonyloxy, benzylcarbonyloxy, etc.), aryloxycarbonyloxy group ( Optionally substituted aryloxycarbonyloxy group, for example, phenoxycarbonyloxy, 3-cyanophenoxycarbonyloxy, 4-acetoxyphenoxycarbonyloxy, 4-t-butoxycarbonylaminophenoxycarbonyloxy, etc.),

Aminocarbonylamino group (optionally substituted aminocarbonylamino group. For example, methylaminocarbonylamino, morpholinocarbonylamino, N-
Ethyl-N-phenylaminocarbonylamino, 4-methanesulfonylaminocarbonylamino, etc., aminocarbonyloxy group (optionally substituted aminocarbonyloxy group. For example, dimethylaminocarbonyloxy, pyrrolidinocarbonyloxy, 4-dipropyl Aminophenylaminocarbonyloxy, etc.), an aminosulfonylamino group (an optionally substituted aminosulfonylamino group, for example, diethylaminosulfonylamino, di-n-butylaminosulfonylamino, phenylaminosulfonylamino, etc.),

A sulfonyloxy group (an optionally substituted sulfonyloxy group, for example, phenylsulfonyloxy, methanesulfonyloxy, chloromethanesulfonyloxy, 4-chlorophenylsulfonyloxy, etc.),
Further, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a halogen atom and the like can be mentioned.

Of these, more preferred groups include an alkoxy group, an amino group, a sulfamoyl group, a sulfonylamino group, a carboxyl group, a sulfo group and a halogen atom.

The Y will be described in more detail below. Y
Include a positive-working relay that releases a photographically useful group in the opposite manner to development.

Examples of the positive-acting relayer include a relayer which exhibits a function when reduced during treatment. Preferred examples of this type of Y include general formula [V]
Is mentioned.

[0037]

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In the general formula [V], EAG represents a group that receives an electron from a reducing substance. N represents a nitrogen atom, W is an oxygen atom, a sulfur atom or -NZ ₁₁ - represents, after EAG receives an electron, the N-W bond is cleaved. Z ₁₁
Represents an alkyl group or an aryl group. Z ₉ and Z _{10 each} represent a mere bond or a substituent other than a hydrogen atom. A solid line represents a bond, and a broken line represents that at least one of them is a bond. G represents [(Dye) _p- X] _q- .

Among the groups represented by the general formula [V], the general formula [VI] is preferable.

[0040]

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In the general formula [VI], O represents an oxygen atom (that is, W in the general formula [V] is an oxygen atom), Z ₁₂ forms a heterocycle containing an N—O bond, and N—O. Represents an atomic group having a property that the Z ₁₂ -G bond is cleaved subsequent to the cleavage of the bond. Z ₁₂ may have a substituent and a saturated or unsaturated ring may be condensed. Z ₁₃ represents —CO— or —SO ₂ —. G represents [(Dye) _p- X] _q- .

A more preferred group of the general formula [VI] is the general formula [VII].

[0043]

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In the general formula [VII], Z ₁₄ represents an alkyl group, an aryl group or an aralkyl group, Z ₁₅ represents a carbamoyl group or a sulfamoyl group, Z ₁₆ represents an alkyl group, an aryl group, an aralkyl group or an alkoxy group, Represents an alkylthio group, an aryloxy group, an arylthio group, a halogen atom, a cyano group or a nitro group, and b is 0 to 3
Represents the integer. The substitution position of the dichloro group in the formula is ortho or para to the nitrogen atom. G is [(Dye)
_p −X] _q −. It is most preferable that Z ₁₅ is a carbamoyl group or a sulfamoyl group substituted with an alkyl group having 12 to 30 carbon atoms.

A specific example of this type of Y is disclosed in JP-A-62-2.
15270 and U.S. Pat. No. 4,783,396.

As another positive-acting releaser which exhibits a reduced function, BEND compounds described in US Pat. Nos. 4,139,379 and 4,139,389, and British Patent 11,445. Listed in Carq
uin compound, JP-A-54-126535, JP-A-57.
-84453.

When these reducible releasers represented by Y represented by the general formula [V] are used, a reducing agent is used in combination, but L containing a reducing group in the same molecule is used.
DA compounds are also included. This is US Pat. No. 4,551,
No. 423.

There is also a type of positive-working releaser that is incorporated as a reductant in a light-sensitive material and deactivates when oxidized during processing. Japanese Patent Application Laid-Open No. 51-63618 and U.S. Pat.
Fields compound described in No. 79 and JP-A-49-11162
No. 8, No. 52-4819, U.S. Pat. No. 4,199,35
The Hinshaw compounds described in No. 4 are mentioned.

As an example of Y of this type, the general formula [VIII]
Can also be mentioned.

[0050]

[Chemical 12]

In the general formula [VIII], Z ₁₇ and Z ₁₉ each independently represent a hydrogen atom or a substituted or unsubstituted acyl group, alkoxycarbonyl group or aryloxycarbonyl group, and Z ₁₈ is an alkyl group. , An aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, or a sulfamoyl group, and Z ₂₀ and Z ₂₁ each independently represent a hydrogen atom, or a substituted or unsubstituted group. Represents an alkyl group, an aryl group, or an aralkyl group. Specifically, it is described in JP-A Nos. 62-245,270 and 63-46450. G represents [(Dye) _p- X] _q- .

A thiazolidine type releaser may be mentioned as a positive-acting releaser having another mechanism. Specifically, it is described in U.S. Pat. No. 4,468,451.

When any of these Y is used as a releaser, it is preferable that Y has at least one ballast group having 10 or more carbon atoms.

Next, the dye portion represented by the general formula [IV] will be described. Preferred examples of R ¹ include substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms (for example, methyl, isopropyl, t-butyl, methoxyethyl, β-cyanoethyl, trifluoromethyl, etc.), and substituted having 1 to 4 carbon atoms. Or an unsubstituted alkoxy group (eg methoxy, ethoxy,
Methoxyethoxy etc.), a substituted or unsubstituted aryl group having 6 to 8 carbon atoms (eg phenyl, p-methoxyphenyl, p-hydroxyphenyl etc.), a hydroxyl group, a cyano group,
Examples thereof include a carbamoyl group and a carboxyl group. Preferred examples of R ² include a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (for example, methyl, butyl, methoxyethyl, β-cyanoethyl, β-acetylaminoethyl, β-methanesulfonylaminoethyl, etc.), and carbon number. 6
~ 8 substituted or unsubstituted aryl group (eg, phenyl, p-methoxyphenyl, p-chlorophenyl, etc.),
A substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl, β-phenethyl, p-methoxyphenethyl, etc.), a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy, methoxyethoxy). Etc.), an acylamino group having 2 to 8 carbon atoms (eg, acetylamino, butyroylamino, pivaloylamino, etc.), a sulfonylamino group having 1 to 7 carbon atoms (eg, methanesulfonylamino, benzenesulfonylamino, etc.) and the like. . Preferred examples of R ³ are hydrogen atom, halogen atom, cyano group, carboxyl group, and 1 to 5 carbon atoms.
A substituted or unsubstituted carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, etc.), a substituted or unsubstituted sulfamoyl group having 0 to 4 carbon atoms (eg, sulfamoyl, N-methylsulfamoyl) , N, N-dimethylsulfamoyl, etc.),
Examples thereof include a substituted or unsubstituted sulfonyl group having 1 to 4 carbon atoms (methanesulfonyl, ethanesulfonyl, etc.), a methyl group, a methoxy group, a methoxyethoxy group and the like.
Dye and X are bonded at any one of R ¹ , R ² and R ³ ,
Those bonded to R ² and R ³ are particularly preferable.

Specific examples of the dye donating compound represented by the general formula [I] used in the color light-sensitive material used in the present invention are shown below, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063] The coating amount of the general formula (I) dye-providing compound represented by the present invention is preferably ^{0.08mmol / m 2 ~0.40mmol / m 2} , 0.12mmol / m 2 ~0.30mmol / m 2 is More preferable.

The compounds represented by the general formulas [II] and [III] are known compounds as sulfonic acid ester and carboxylic acid ester, respectively. For details, see US Pat. No. 5,051,348, page 5 to
It is described on page 8. In the present invention, these compounds are used as acid precursors. An acid precursor is defined as a compound that releases an acid upon heat or hydrolysis.

Specific examples of the acid precursors represented by the general formulas [II] and [III] used in the color light-sensitive material used in the present invention are shown below, but the present invention is not limited thereto.

[0066]

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[0067]

[Chemical 21]

[0068]

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[0069]

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[0070]

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The coating amount of the acid precursor represented by the general formulas [II] and [III] of the present invention is the base precursor described below.
Preferably 0.001mol / m ² ~1mol / m ² to 1 mol, 0.005 mol
/ m ^{2 to} 0.2 mol / m ² is more preferable.

As the halogen composition of the silver halide emulsion of the present invention, any silver halide such as silver iodobromochloride, silver iodochloride, silver chlorobromide and silver chloride may be used, and particularly silver chlorobromide. Is preferred.

The silver halide emulsion may have various shapes. Examples of them are cubes,
Examples thereof include regular grains having a regular crystal form such as octahedron and tetradecahedron, tabular grains, spherical grains and grains having an irregular crystal form such as potato grains.

The halogen composition in the grains may be uniform, the inside and the outside may have different halogen compositions, or may have a layered structure. (JP-A-57-1452
No. 32, No. 58-108533, No. 58-248469, No. 59-48755,
59-52237, U.S. Pat.Nos. 3,505,068 and 4,433,048.
No. 4,444,877, European Patent No. 100,984, and British Patent No. 1,027,146).

The silver halide emulsion may be monodisperse or polydisperse, and a mixture of monodisperse emulsions may be used. The particle size is preferably 0.01 μm to 10 μm, particularly preferably 0.1 μm to 3 μm. Here, a monodisperse silver halide emulsion is defined as one in which 95% or more of the total weight or the total number of silver halide grains contained therein is within ± 40% of the average grain size, more preferably within ± 30%. It

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion can be used as a direct reversal emulsion in combination with a nucleating agent or a light fogging.

In the present invention, two or more kinds of silver halide emulsions having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like can be used in combination, and different emulsion layers and / or the same emulsion layer can be used. Can be used for

The photothermographic material used in the present invention basically has a photosensitive silver halide and a binder on a support, and further, if necessary, an organometallic salt oxidizing agent,
A dye donating compound or the like can be included. These components are often added to the same layer, but may be added separately to another layer if they can react.
For example, if a dye-donating compound which is colored is present in the lower layer of the silver halide emulsion, it prevents the sensitivity from lowering. The reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

The silver halide emulsion used in the present invention is subjected to various chemical sensitizations on the grain surface of the silver halide emulsion. The above chemical sensitization is written by James, The Theory of Photographic Process, 4th edition, published by Macmillan, 1977, (THJames, The Theory of the Photogra
Phic Process, 4th ed, Macmillan, 1977) with active gelatin as described on pages 67-76, and Research Disclosure 120, 1974.
April, 12008; Research Disclosure 34, 19
June 1975, 13452, U.S. Pat.Nos. 2,642,361 and 3,297,
No. 446, No. 3,772,031, No. 3,857,711, No. 3,90
1,714, 4,266,018 and 3,904,415, and pAg5-1 as described in British Patent 1,315,755.
Sulfur, selenium, at 0, pH 5-8 and temperature 30-80 ° C
It can be carried out using tellurium, gold, platinum, palladium, iridium, rhodium or combinations of these sensitizers.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. . For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. For the photothermographic material,
Various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer can be provided.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60-1
A silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate described in JP-A-13235;
The acetylene silver described in No. 249044 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salts are
0.01 to 10 per mole of photosensitive silver halide
Mole, preferably 0.01 to 1 mole. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978) pages 24 to 25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or JP-A-59-111636, A mercapto compound and a metal salt thereof described in JP-A-4-73649, JP-A-62.
The acetylene compounds described in JP-A-87957 and JP-A-4-255845 are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (1978
Year) sensitizing dyes described on pages 12 to 13 and the like. These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 61
5,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, and US Pat.
83,756 and 4,225,666, before or after nucleation of silver halide grains. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing element. Examples thereof include those described in JP-A-62-253159, pages (26) to (28). Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, a protein such as a gelatin derivative or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol,
Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. In addition, JP-A-62-1
No. 245260, etc., namely, a superabsorbent polymer, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a copolymerization of the vinyl monomers with each other or with other vinyl monomers. Combined (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5 manufactured by Sumitomo Chemical Co., Ltd.)
H) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. Especially,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

As the electron donor used in the present invention, those known in the field of photothermographic materials can be used. Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of electron donors used in the present invention include US Pat. No. 4,500,626.
No. 49 to 50, No. 4,483,914, No. 30 to 31, No. 4,330,617, No. 4,590,152, and JP-A-60-140335 (17) to (18). ), Ibid. 57-40
245, 56-138736, 59-1784.
No. 58, No. 59-53831, No. 59-182449.
No. 59-182450, No. 60-119555
Nos. 60-128436 to 60-128439
No. 60-198540, 60-18174
No. 2, No. 61-259253, No. 62-244044.
No. 62-131253 to 62-131256
Up to No. 220,746A2, pages 78 to 96, there are electron donors and electron donor precursors.
Various electron donor combinations, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

The electron transfer agent or its precursor can be selected from the above-mentioned electron donors or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion-resistant electron donor. Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant electron donor used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the above-mentioned reducing agents, and preferably hydroquinones and sulfonamidephenols. , Sulfonamide naphthols, and compounds described as electron donors in JP-A No. 53-110827. In the present invention, the total amount of the electron donor and the electron transfer agent is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

In the present invention, the development inhibitor releasing redox compound can be used as described above. For example, JP
1-213847, 62-260153, JP-A-2-68547, 2-110557, 2-25.
Those described in No. 3253 and No. 1-150135 can be used. A method for synthesizing the development inhibitor releasing redox compound used in the present invention is described in, for example, JP-A-61-21.
3847, 62-260153, U.S. Pat.
684,604, JP-A-1-269936, US Pat. Nos. 3,379,529, and 3,620,746,
4,377,634, 4,332,878, JP-A-49-129536, 56-153336,
No. 56-153342.

The development inhibitor-releasing redox compound of the present invention contains 1 × 10 ^{−6 to} 5 × 10 ⁻² per mol of silver halide.
Mole, more preferably in the range of 1 × 10 ^-5 to 1 × 10 ^-2 mole. The development inhibitor releasing redox compound used in the present invention may be any suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. And methylcellosolve. Also, by an already well-known emulsification dispersion method, dibutyl phthalate, trisyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion. Can be created and used. Alternatively, the powder of the development inhibitor-releasing redox compound may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The heat-developable color light-sensitive material of the present invention contains at least one of dextran, pullulan and derivatives thereof. Dextran and pullulan are a kind of polysaccharides.
-A polymer of glucose. The dextran used in the present invention preferably has a molecular weight of 20,000 to 2,000,000.
Those having a molecular weight of 100,000 to 800,000 are preferable. Pullulan is 20,000 ~
Two million are preferred. Examples of the dextran or pullulan derivative include those obtained by introducing a sulfinic acid group, an amino group, or the like into dextran or pullulan so as to easily react with a hardening agent. Dextran, pullulan and derivatives thereof may be used alone or in combination of two or more. The layer containing dextran, pullulan and derivatives thereof may be any layer of the photothermographic material, but it is preferably contained in the intermediate layer or the protective layer. Dextran, pullulan and / or a derivative thereof are used in an amount of 0.01 to 10 g / m ² , preferably 0.05 to 10 g / m ² .
It is in the range of 5 g / m ² . If the amount is less than 0.01 g / m ² , the present invention is not effective and the range of use is 10
If it exceeds g / m ² , the film quality will be deteriorated.

Hydrophobic additives such as dye-donor compounds, antidiffusive reducing agents and electron donors are described in US Pat. No. 2,322,0.
It can be incorporated into the layer of the light-sensitive material by a known method such as the method described in No. 27. In this case, JP-A-59
-83154, 59-178451, 59-1
78452, 59-178453, 59-17.
No. 8454, No. 59-178455, No. 59-178.
A high boiling point organic solvent as described in No. 457 and the like can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-donating compound used. Also, 1 g per 1 g of binder
cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable.

JP-B-51-39853, JP-A-51-
The dispersion method using a polymer described in 59943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,62.
No. 6, columns 51 to 52.

A dye fixing element is used together with a light-sensitive material in a system for forming an image by diffusion transfer of a dye. The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in US Pat. No. 4,500,626, column 57 can be applied to the present invention.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626.
Nos. 58-59 and JP-A-61-88256 (32)-(41)
The mordant described in the above pages, JP-A Nos. 62-244043 and 6
Examples thereof include those described in No. 2-244036. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. The dye-fixing element may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing element. A specific example is JP-A-62-253159 (25).
Page, pp. 62-245253, and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicones (trade name X-2).
2-33710) is effective. Further, Japanese Patent Application Laid-Open No. Sho 62-2
The silicone oils described in 15953 and 63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, 4,254,195, columns 3 to 8, and JP-A-62-174741. No. 61-88256 No. (2
7) to (29), 63-199248, JP-A-1-75.
There are compounds described in Nos. 568 and 1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272, pages 125-137. An anti-fading agent for preventing fading of the dye transferred to the dye fixing element may be contained in the dye fixing element in advance,
The dye fixing element may be supplied from the outside such as a light-sensitive material. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other. A fluorescent whitening agent may be used for the light-sensitive material and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive material. As an example, K. Veenkataraman ed. "The Chemistry of Syntheti
c Dyes ”, Volume V, Chapter 8, and compounds described in JP-A-61-143752. More specifically, stilbene compounds, coumarin compounds,
Examples thereof include biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 41 is used.
Column, JP-A-59-116655 and JP-A-62-24526.
The hardeners described in No. 1 and No. 61-18942 are listed. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-
Examples thereof include methylol type hardeners (dimethylolurea etc.) and polymer hardeners (compounds described in JP-A-62-234157). Particularly preferably, JP-A-3-
The vinyl sulfone type hardener described in 114043 is used.

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
And No. 62-183457. The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-209 can be used.
No. 44, No. 62-135826, or the like, or a fluorine-containing surfactant such as a fluorine-containing surfactant such as a fluorine-containing compound such as a fluorine oil or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used for the light-sensitive material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
1-88256, in addition to the compound described on page (29), benzoguanamine resin beads, polycarbonate resin beads,
There are compounds such as AS resin beads described in JP-A-63-274944 and JP-A-63-274952. In addition, the constituent layers of the light-sensitive material and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-88256.
No. (26)-(32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.
Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are U.S. Pat. No. 4,511,493,
It is described in JP-A-62-65038.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye fixing element in order to improve the storage stability of the light-sensitive material. In the present invention, EP 210,660, U.S. Pat.
Use is made of a combination of the hardly soluble metal compound described in No. 45 and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound). Specifically, it is described in JP-A-2-269338, pages (2) to (6). Particularly preferred compounds as the sparingly soluble metal compound are zinc hydroxide, zinc oxide and a mixture of both.

In the present invention, various development stopping agents can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide are further prepared from polypropylene. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition, the supports described in JP-A No. 62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and an electric field, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP). ), An inorganic compound represented by lithium iodate, BaB ₂ O ₄ or the like, a urea derivative, a nitroaniline derivative, for example, nitropyridine-N-such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivative, JP-A-6
Compounds described in 1-53462 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. Further, the image information is
Image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), image signals obtained by dividing an original image into a large number of pixels such as a scanner, CG, CAD, etc. An image signal created by using a computer can be used.

The light-sensitive material and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of dye. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
No. 45544 can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., but development at about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably not lower than 50 ° C. and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C. or more and 100 ° C. or less. Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (for these bases, an image). The one described in the section of the formation accelerator is used)
Can be mentioned. Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the light-sensitive material or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film). Examples of the method for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (2).
There is a method described on page 6). Further, the solvent can be used by being incorporated in advance in the light-sensitive material or the dye-fixing element or both in the form of enclosing the solvent in microcapsules.

Further, in order to promote dye transfer, a system in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive material or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye-fixing layer, but is preferably incorporated in the dye-fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

As the heating method in the developing and / or transferring step, a heated block or plate may be contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. may be contacted. And passing through a high temperature atmosphere. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
No. 44, JP-A-3-131856 and JP-A-3-13185
The device described in No. 1 or the like is preferably used.

[0115]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

Example 1 A method for preparing a zinc hydroxide dispersion will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described.

10 g of the following electron transfer agent and 0.5 of polyethylene glycol nonyl phenyl ether as a dispersant
g, the following anionic surfactant (0.5 g) was added to a 5% aqueous gelatin solution, and the mixture was milled for 60 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0120]

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[0121]

[Chemical formula 26]

Next, a method for preparing a dispersion of the dye trapping agent will be described.

The following polymer latex (solid content 9%)
108 ml, the following surfactants 18.3 g, water 1188 ml
While stirring the mixed solution of, the following anionic surfactant
657 ml of 4.2% aqueous solution of (2) was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Then 1500ml
And the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0124]

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[0125]

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[0126]

[Chemical 29]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Cyan, magenta, and yellow dye-donor compounds and electron-donor gelatin dispersions were prepared according to the formulations shown in Table 1. That is, each oil phase component was dissolved by heating at about 60 ° C to form a uniform solution, this solution and the water phase component heated at about 60 ° C were added, and the mixture was stirred and mixed and then homogenized with a homogenizer.
Dispersed for 3 minutes at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0129]

[Table 1]

[0130]

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[0131]

[Chemical 31]

[0132]

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[0133]

[Chemical 33]

[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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Next, a method for preparing a gelatin dispersion of the hydrophobic additive of the present invention will be described. The above-mentioned dye-donor compound
A gelatin dispersion of a dye-donor compound was prepared in the same manner except that the compounds Y-10 and Y-19 of the present invention were used instead of (4).

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and the following chemicals in 673 ml of water). (A) Add 15mg and 40 ℃
Solution (I) and solution (II) in Table 2 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, (II in Table 2
Solution (I) and solution (IV) were added simultaneously at the same flow rate for 32 minutes.
In addition, 20 minutes after the addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (190 ml of water in which gelatin was 1.8
g, the following pigment (a) 127 mg, the following pigment (b) 25
2 mg, containing 9 mg of the following dye (c) and kept at 45 ° C.) were added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 68 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.22 μm was obtained.

[0148]

[Table 2]

[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 5 g of sodium chloride in 693 ml of water).
g and the above-mentioned chemical (A) (15 mg) and the mixture was kept at 54 ° C.), the solutions (I) and (II) shown in Table 3 were added over 10 minutes. After 5 minutes, solution (III) and solution (IV) shown in Table 3 were added over 30 minutes. Also, 18 minutes after the addition of the liquids (III) and (IV) is started, an aqueous solution of a gelatin dispersion of the dye (1.0 g of gelatin in 105 ml of water, 70 g of the above-mentioned dye (a)) is added.
mg, the pigment (b) 139 mg, the pigment (c) 5 mg
Was added and kept at 45 ° C.) for 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene is added, then sodium thiosulfate and chloroauric acid are added to optimize chemical sensitization at 68 ° C,
Next, the antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.43 μm was obtained.

[0156]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 4 parts of sodium chloride)
g) and 15 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 47 ° C.). Solution (I) and solution (II) in Table 4 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) shown in Table 4 were simultaneously added at the same flow rate for 32 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of a gelatin dispersion of the dye (2.5 g of gelatin in 100 ml of water and 250 mg of the following dye (d) and kept at 45 ° C.) is collectively added. Was added.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0159]

[Table 4]

[0160]

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Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 60 ° C.).
Add at an equal flow rate for minutes. After 10 minutes, solution (III) and solution (IV) shown in Table 5 were added simultaneously at the same flow rate for 20 minutes. Also (I
1) One minute after the completion of the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a dye (1.8 g of gelatin in 75 ml of water and 180 mg of the above-mentioned dye (d) and kept at 45 ° C.) is collected at a time. Was added.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0163]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g) and 15 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 51 ° C.). Solution (I) and solution (II) shown in Table 6 were simultaneously added at the same flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) in Table 6 were simultaneously added at the same flow rate for 32 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 9
235 mg of the following dye (e) in 5 ml and 5 ml of methanol
And the following dye (f) containing 120 mg and kept at 45 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0166]

[Table 6]

[0167]

Embedded image

[0168]

[Chemical 51]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 695 ml of water).
g and 15 mg of the above-mentioned chemical (A), and kept at 63 ° C.).
Add at an equal flow rate for minutes. After 10 minutes, solutions (III) and (IV) in Table 7 were simultaneously added at an equal flow rate for 30 minutes. Also (I
One minute after the completion of the addition of the liquids (II) and (IV), an aqueous solution of the dye (water 6
155 mg of the above dye (e) in 6 ml and 4 ml of methanol.
And 78 mg of the above-mentioned dye (f) and kept at 60 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.52 μm was obtained.

[0171]

[Table 7]

Photosensitive materials 101 shown in Tables 8 to 10 were prepared using the above materials.

[0173]

[Table 8]

[0174]

[Table 9]

[0175]

[Table 10]

[0176]

Embedded image

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

[0180]

Embedded image

Photosensitive material except that the compounds S-1 and S-2 of the present invention are added to the first layer and / or the third layer from the light-sensitive material 101 or the dye-donor compound of the fifth layer is changed. The light-sensitive material 102 shown in Table 11 in exactly the same manner as the material 101.
I made ~ 110.

[0182]

[Table 11]

Next, how to make the image receiving material will be described.

An image receiving material R101 having a constitution as shown in Tables 12 to 13 was prepared.

[0185]

[Table 12]

[0186]

[Table 13]

[0187]

Embedded image

[0188]

Embedded image

[0189]

Embedded image

Using the photosensitive materials 101 to 110 and the image receiving material R101 described above, processing was performed using Pyritrostat 300 manufactured by Fuji Photo Film Co., Ltd. That is, an original image [a test chart on which Y, M, C, B, G, R, and gray wedges whose densities are continuously changing is recorded] is scanned and exposed through a slit, and the exposed photosensitive material is exposed to 40 After immersing in water kept at ℃ for 2.5 seconds, it was squeezed with a roller and immediately superposed so that the image receiving material and the film surface were in contact with each other. Then, each photosensitive material was heated for 17 seconds and the photosensitive material was peeled off from the image receiving material using a heat drum whose temperature was adjusted so that the temperature of the absorbed film surface became 80 ° C. An excellent color image was obtained.

The density of each of these color images was measured using a density measuring device X Light 404 manufactured by X Light Co. Photosensitive material 1
Table 14 shows the measurement results of the minimum densities (Dmin) of yellow, magenta, and cyan for 01 to 110, the cyan density of red, and the magenta density of green.

[0192]

[Table 14]

Regarding the color reproducibility of green and red, the color purity is improved and the color reproducibility is improved as the magenta and cyan densities, which are the complementary colors, decrease. In the case of the light-sensitive material of the present invention,
It can be seen that the magenta density in green and the cyan density in red are lowered, and the color reproducibility is improved. Also, as Dmax is larger and Dmin is smaller, the discrimination is improved, and in particular, the value of Dmin is as sharp as a human sense and only 0.0
A large difference of 1 is identified as a white background difference. In the case of the light-sensitive material of the present invention, Dmax is high and Dmin is low, which shows that the discrimination is improved.

Then, the above-mentioned photosensitive materials 101 to 110 were left for 3 days in a state of being rolled into a celco whose humidity was adjusted to 45 ° C. and 80% RH to conduct a forced test. The light-sensitive material and the image-receiving material were processed in the same manner as above, and the same density measurement as described above was performed on these light-sensitive materials. The results are shown in Table 15.

[0195]

[Table 15]

When left at 45 ° C. and 80% RH for 3 days, Dmax decreases and Dmin increases. That is, the discrimination becomes worse, which is not preferable, and the difference (ΔDmax,
It is desired that ΔDmin) is small. In the case of the light-sensitive material of the present invention, both are improved, and it is understood that the raw storability is excellent.

[0197]

According to the present invention, a heat-developable color light-sensitive material having good color reproducibility, low minimum density and excellent raw storage stability can be obtained.

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[Procedure amendment]

[Submission date] September 28, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Using the photosensitive materials 101 to 110 and the image receiving material R101 described above, processing was performed using Pictrostat 300 manufactured by Fuji Photo Film Co., Ltd. That is, an original image [a test chart on which Y, M, C, B, G, R, and gray wedges whose densities are continuously changing is recorded] is scanned and exposed through a slit, and the exposed photosensitive material is exposed to 40 After immersing in water kept at ℃ for 2.5 seconds, it was squeezed with a roller and immediately superposed so that the image receiving material and the film surface were in contact with each other. Then, each photosensitive material was heated for 17 seconds and the photosensitive material was peeled off from the image receiving material using a heat drum whose temperature was adjusted so that the temperature of the absorbed film surface became 80 ° C. An excellent color image was obtained.

Claims (1)

[Claims] 1. At least a light-sensitive silver halide, a binder, an electron transfer agent and / or a precursor thereof, an electron donor and / or a precursor thereof, and a reducible substance which is reduced to release a diffusible dye on a support. Heat-developable color light-sensitive material having at least one layer containing an organic dye-donating compound, and having a layer containing at least one compound represented by the following general formula [I], and the same layer as the layer. And / or another layer containing at least one compound represented by the following general formulas [II] and [III]. Embedded image Embedded image Embedded image In the general formula [I], Dye represents a dye group or a dye precursor group represented by the following general formula [IV]. Y is a group having a property of causing a difference in diffusivity of a group functioning as a development inhibitor after the photosensitive silver halide having an imagewise latent image is released corresponding to reduction to silver. And X represents a simple bond or a linking group. p represents a natural number of 1 or more, and q represents 1 or 2. When p is 2 or more or q is 2, Dye or (Dye) _p -X may be the same or different. Embedded image In the formula, R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a hetero group. It represents a substituent selected from a ring group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, a sulfonylamino group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkylthio group and an arylthio group. R
₃ exclude hydrogen atoms defined in R _1, R ₂ others, R _1,
Synonymous with R ₂ . n represents an integer of 0 to 5, and n is 2 to
When 5, R ₃ may be the same or different. Dy
e and X are bonded by any _one of R ₁ , R ₂ and R _{3 in} the general formula [IV].